CN1894198A - Process for producing dialkyl alpha-fluoromalonates - Google Patents
Process for producing dialkyl alpha-fluoromalonates Download PDFInfo
- Publication number
- CN1894198A CN1894198A CNA200480023543XA CN200480023543A CN1894198A CN 1894198 A CN1894198 A CN 1894198A CN A200480023543X A CNA200480023543X A CN A200480023543XA CN 200480023543 A CN200480023543 A CN 200480023543A CN 1894198 A CN1894198 A CN 1894198A
- Authority
- CN
- China
- Prior art keywords
- triethylamine
- hydrogen fluoride
- formula
- alpha
- mole
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 34
- RBCXEDQEZDUMHD-UHFFFAOYSA-N 2-fluoropropanedioic acid Chemical class OC(=O)C(F)C(O)=O RBCXEDQEZDUMHD-UHFFFAOYSA-N 0.000 title abstract description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 55
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 19
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 11
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 150000002148 esters Chemical class 0.000 description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- -1 dicarbonyl compound Chemical class 0.000 description 4
- 150000003230 pyrimidines Chemical class 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- GOWQBFVDZPZZFA-UHFFFAOYSA-N diethyl 2-fluoropropanedioate Chemical compound CCOC(=O)C(F)C(=O)OCC GOWQBFVDZPZZFA-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 125000005270 trialkylamine group Chemical group 0.000 description 2
- 230000000975 bioactive effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- IKGLACJFEHSFNN-UHFFFAOYSA-N hydron;triethylazanium;trifluoride Chemical compound F.F.F.CCN(CC)CC IKGLACJFEHSFNN-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/307—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to an advantageous process for the production of novel dialkyl alpha-fluoromalonates.
Description
The present invention relates to novel helping and produce the method for alpha-fluoromalonic acid dialkyl esters.
Alpha-fluoromalonic acid dialkyl esters is for example to be used to produce 4, the intermediates of 6-two chloro-5-fluorinated pyrimidines (referring to EP-A-0970057).4,6-two chloro-5-fluorinated pyrimidines are important intermediates of producing active substance, and this active substance is as plant protectant (referring to EP-A-0882043 and EP-A-0937050).
Known, the alpha-fluoro-beta-ketoester of formula (I) is that the adduct by the alpha-chloro-beta-ketoester of formula (II) and hydrogen fluoride and trialkylamine reacts acquisition, and reaction is carried out adding to depress, and temperature of reaction is 103-130 ℃.
A main drawback of this method is to depress the cost of equipment that processing need improve adding, and needs special technical safety measures.Because have these deficiencies, this method is not suitable for large-scale industrial application.
In another kind of method (referring to DE-A-4237882), the alpha-fluoro-beta-dicarbonyl compound of formula (B) is that the adduct by the dicarbonyl compound of formula (A) and hydrogen fluoride and trialkylamine reacts acquisition, and temperature of reaction is 20-100 ℃.
The shortcoming of this method is a long reaction time required when producing alpha-fluoromalonic acid dialkyl esters, still is 72 hours even use a large amount of excessive hydrogen fluoride and triethylamine reaction times.
The present task of the present invention provides the method for producing alpha-fluoromalonic acid dialkyl esters, still can provide high productive rate and shorter reaction times even the excessive amount of this method hydrogen fluoride and triethylamine is little under the overpressure situation not applying, and has improved the space-time yield thus.Finding that particularly this method consumes a spot of raw material, is a kind of environment-friendly type method.
The alpha-fluoromalonic acid dialkyl esters of finding general formula (I) now obtains by following method:
Wherein:
R
1The alkoxyl group that representative has a 1-4 carbon atom with
R
2Represent hydrogen or fluorine,
Comprise that the dicarbonyl compound that makes general formula (II) and the adduct of hydrogen fluoride and triethylamine react under 103-115 ℃ temperature,
Wherein:
R
1Have above-mentioned definition and
R
3Represent hydrogen, fluorine or chlorine.
In the compound of formula (II), R
1Preferred representation methoxy or oxyethyl group.
In the compound of formula (II), R
1Especially preferably represent oxyethyl group.
In the compound of formula (I), R
2The preferred hydrogen of representing.
Group above-mentioned or that provide in preferable range both had been applicable to the initial compounds of formula (II), also was applicable to the final product of formula (I).
The most unexpected part of the present invention is that method of the present invention can carry out under the only excessive slightly condition of normal pressure and hydrogen fluoride and triethylamine, and space-time yield has improved 10 times.The productive rate of special alpha-fluoromalonic acid dialkyl esters surprisingly is the same high with the method production of pressing description of the Prior Art, and existing method is carried out under normal pressure and low temperature, because the professional thinks that part can take place decomposes, and causes productive rate to reduce under comparatively high temps.
Method of the present invention has a series of advantage.Like this, the reaction times of alpha-fluoromalonic acid dialkyl esters has only accounted for a part of producing by currently known methods under normal pressure.By method of the present invention, the reaction times is 15 hours, need 72 hours (referring to DE-A4237892) and press the currently known methods reaction times.Though particularly importantly reaction can be carried out under normal pressure, has obtained good space-time yield.Although another advantage is that the reaction times is shorter, it is excessive slightly that hydrogen fluoride and triethylamine only need.Therefore, this novel method is specially adapted to large-scale industrial production.
The dicarbonyl compound of general formula (II) and other all initial compounds are conventional commercially available prod, or prepare by simple method.
When carrying out method of the present invention, usually use the adduct of hydrogen fluoride and triethylamine, every mole triethylamine contains the hydrogen fluoride of 1-2 mole in the adduct, and preferred every mole triethylamine contains the hydrogen fluoride of 1.2-1.8 mole, the hydrogen fluoride of preferred especially 1.4-1.5 mole.
For carrying out method of the present invention, the initial compounds of common every mole formula (III) uses the triethylamine conduct and hydrofluoric adduct of 1-4 mole, preferred 1.2-2.5 mole, preferred especially 1.4-2 mole.
The adduct of hydrogen fluoride and triethylamine can be produced by triethylamine being mixed in the liquid hydrogen fluoride on the spot.The adduct of hydrogen fluoride and triethylamine also can obtain by hydrogen fluoride is incorporated in the triethylamine on the spot.
When carrying out method of the present invention, temperature of reaction changes in narrower scope.Usually be 103-115 ℃ in temperature of reaction, preferred temperature is 105-110 ℃ of operation down.
Method of the present invention is carried out under normal pressure.Normal pressure among the present invention is meant 800-1200mbar pressure.
Usually carry out method of the present invention in the following manner: the adduct that in a reaction vessel, adds hydrogen fluoride and triethylamine.At once or heating down to the dicarbonyl compound that wherein is metered into general formula (II).The reacting by heating mixture stirs to 105-110 ℃ then.Then cool off, add entry.Separate organic phase, the optional distillation.In order from water, to isolate product better, can advantageously use the extraction agent of a times or many times.For example can use dimethylbenzene, toluene or methylene dichloride.
Preferably, under temperature of reaction, continue to stir up to obtaining best productive rate.
Method of the present invention for example is used to produce the alpha-fluoromalonic acid diethyl ester, and this compound for example can be used as produces 4, the intermediate product (referring to EP-A-970057) of 6-two chloro-5-fluorinated pyrimidines.4,6-two chloro-5-fluorinated pyrimidines are used for producing the heterocycle that fluorine replaces, and described heterocycle for example is bioactive or is hopeful intermediate product (referring to N.Ishikawa, J.Fluorine Chem.1984,25,203, or EP-A970057) as plant protectant.
The following examples are intended to illustrate the present invention.But the present invention is not limited to this embodiment.
Preparation embodiment
Embodiment 1 alpha-fluoromalonic acid diethyl ester
Add 137 gram (0.85 mole) triethylamine-trihydrofluoride, under 80 ℃, restrain (0.85 mole) triethylamines to wherein adding 86.Then in 2 hours, being metered into 195 gram (1 mole) alpha-chloro diethyl malonates under 80 ℃.Then under normal pressure, reflux and stir 15 hours (105-110 ℃).For the reaction product of emanating, in 60 ℃ of downhill reaction mixtures, add 200 gram dimethylbenzene, add 215 gram water then, under 60 ℃, isolate this phase then.Contain water with 100 gram xylene extraction.
Merge two kinds of organic phases, under vacuum, distill.First cut is a dimethylbenzene.Second cut (156 gram) contains 96% alpha-fluoromalonic acid diethyl ester.Its amount is 0.84 mole, and perhaps productive rate is 84%.
Claims (6)
1. produce the method for general formula (I) compound
Wherein:
R
1The alkoxyl group that representative has a 1-4 carbon atom with
R
2Represent hydrogen or fluorine,
The adduct that it is characterized in that making the compound of general formula (II) and hydrogen fluoride and triethylamine reacts under 103-115 ℃ temperature and normal pressure,
Wherein:
R
1Have above-mentioned definition and
R
3Represent hydrogen, fluorine or chlorine.
2. according to the method for claim 1, it is characterized in that in formula (I) and compound (II) R
1Representation methoxy or oxyethyl group.
3. according to the method for at least one of claim 1-2, it is characterized in that in formula (I) and (II), R
2And R
3Represent hydrogen respectively.
4. according to the method for at least one of claim 1-3, it is characterized in that method is to carry out under 105-110 ℃ temperature.
5. according to the method for at least one of claim 1-4, it is characterized in that every mole of triethylamine contains the 1-2 moles of hydrogen fluoride in the adduct of hydrogen fluoride and triethylamine.
6. according to the method for at least one of claim 1-5, it is characterized in that using the triethylamine of 1-4 mole by the compound of formula (II).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10337885.5 | 2003-08-18 | ||
| DE10337885A DE10337885A1 (en) | 2003-08-18 | 2003-08-18 | Process for the preparation of α-fluoromalonic acid dialkyl esters |
| PCT/EP2004/009117 WO2005019154A1 (en) | 2003-08-18 | 2004-08-13 | METHOD FOR PRODUCING α-FLUOROMALONIC ACID DIALKYL ESTERS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1894198A true CN1894198A (en) | 2007-01-10 |
| CN1894198B CN1894198B (en) | 2012-07-18 |
Family
ID=34201625
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200480023543XA Expired - Lifetime CN1894198B (en) | 2003-08-18 | 2004-08-13 | Process for producing dialkyl alpha-fluoromalonates |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US7807851B2 (en) |
| EP (2) | EP2261198A1 (en) |
| JP (3) | JP2007502793A (en) |
| KR (1) | KR101167233B1 (en) |
| CN (1) | CN1894198B (en) |
| BR (1) | BRPI0413686B1 (en) |
| DE (1) | DE10337885A1 (en) |
| DK (1) | DK1658259T3 (en) |
| ES (1) | ES2392051T3 (en) |
| IL (1) | IL173773A (en) |
| WO (1) | WO2005019154A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104418739A (en) * | 2013-08-19 | 2015-03-18 | 上海元符医药科技有限公司 | Synthetic method of 2-fluorodimethyl malonate (I) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1942087A1 (en) * | 2005-10-05 | 2008-07-09 | Daiichi Sankyo Company, Limited | Method for dehydrohalogenation of organic halogen compound |
| JP5642394B2 (en) * | 2010-01-07 | 2014-12-17 | 日本曹達株式会社 | Method for producing fluorinated disulfide compound |
| AR100015A1 (en) | 2013-07-08 | 2016-09-07 | Arysta Lifescience Corp | PROCEDURE TO PREPARE FLUOXASTROBIN |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2823969A1 (en) | 1978-06-01 | 1979-12-13 | Hoechst Ag | PROCESS FOR PRODUCING ORGANIC FLUORINE COMPOUNDS |
| JPS61180727A (en) * | 1985-02-07 | 1986-08-13 | Tokuyama Soda Co Ltd | Production of aromatic compound having chlorodifluoromethyl group |
| DE4237892C2 (en) | 1992-11-10 | 1999-02-04 | Peter Wohland | Dispenser for evaporable fragrances and remedies |
| DE4237882A1 (en) * | 1992-11-10 | 1994-05-11 | Bayer Ag | Process for the preparation of alpha-fluoro-beta-dicarbonyl compounds |
| DE19602095A1 (en) | 1996-01-22 | 1997-07-24 | Bayer Ag | Halopyrimidines |
| JP3882856B2 (en) * | 1996-05-16 | 2007-02-21 | 旭硝子株式会社 | Method for producing α-fluoro-β-ketoester |
| DE19646407A1 (en) | 1996-11-11 | 1998-05-14 | Bayer Ag | Halopyrimidines |
| DE19710609A1 (en) | 1997-03-14 | 1998-09-17 | Bayer Ag | Substituted aminosalicylic acid amides |
| JP3496460B2 (en) * | 1997-06-13 | 2004-02-09 | ダイキン工業株式会社 | Electrolytic solution and lithium secondary battery using the same |
| DE10041618A1 (en) * | 2000-08-24 | 2002-03-07 | Bayer Ag | Process for the preparation of alpha-fluoro-malonic acid dialkyl esters |
| DE10104663A1 (en) * | 2001-02-02 | 2002-08-08 | Solvay Fluor & Derivate | Production of fluorine compounds |
-
2003
- 2003-08-18 DE DE10337885A patent/DE10337885A1/en not_active Withdrawn
-
2004
- 2004-08-13 EP EP10175679A patent/EP2261198A1/en not_active Withdrawn
- 2004-08-13 JP JP2006523586A patent/JP2007502793A/en not_active Withdrawn
- 2004-08-13 WO PCT/EP2004/009117 patent/WO2005019154A1/en active Application Filing
- 2004-08-13 BR BRPI0413686-1A patent/BRPI0413686B1/en active IP Right Grant
- 2004-08-13 US US10/568,355 patent/US7807851B2/en active Active
- 2004-08-13 DK DK04764111.3T patent/DK1658259T3/en active
- 2004-08-13 ES ES04764111T patent/ES2392051T3/en not_active Expired - Lifetime
- 2004-08-13 CN CN200480023543XA patent/CN1894198B/en not_active Expired - Lifetime
- 2004-08-13 EP EP04764111A patent/EP1658259B1/en not_active Expired - Lifetime
- 2004-08-13 KR KR1020067003271A patent/KR101167233B1/en active IP Right Grant
-
2006
- 2006-02-16 IL IL173773A patent/IL173773A/en active IP Right Grant
-
2013
- 2013-06-28 JP JP2013136316A patent/JP2013241421A/en active Pending
-
2014
- 2014-01-30 JP JP2014015157A patent/JP2014139174A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104418739A (en) * | 2013-08-19 | 2015-03-18 | 上海元符医药科技有限公司 | Synthetic method of 2-fluorodimethyl malonate (I) |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2392051T3 (en) | 2012-12-04 |
| EP1658259B1 (en) | 2012-07-25 |
| KR20060065699A (en) | 2006-06-14 |
| JP2014139174A (en) | 2014-07-31 |
| EP1658259A1 (en) | 2006-05-24 |
| DE10337885A1 (en) | 2005-03-24 |
| WO2005019154A1 (en) | 2005-03-03 |
| DK1658259T3 (en) | 2012-11-12 |
| US20070191628A1 (en) | 2007-08-16 |
| BRPI0413686B1 (en) | 2015-02-10 |
| JP2013241421A (en) | 2013-12-05 |
| IL173773A0 (en) | 2006-07-05 |
| US7807851B2 (en) | 2010-10-05 |
| IL173773A (en) | 2011-08-31 |
| KR101167233B1 (en) | 2012-07-23 |
| BRPI0413686A (en) | 2006-10-24 |
| CN1894198B (en) | 2012-07-18 |
| EP2261198A1 (en) | 2010-12-15 |
| JP2007502793A (en) | 2007-02-15 |
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| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170713 Address after: German Monheim Patentee after: BAYER INTELLECTUAL PROPERTY GmbH Address before: German Monheim Patentee before: BAYER CROPSCIENCE AG |
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| TR01 | Transfer of patent right | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 50 Alfred Nobel Street, Monheim, Rhine, Germany 40789 Patentee after: BAYER INTELLECTUAL PROPERTY GmbH Address before: Germany Patentee before: BAYER INTELLECTUAL PROPERTY GmbH |
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| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240112 Address after: 50 Alfred Nobel Street, Monheim, Rhine, Germany 40789 Patentee after: BAYER CROPSCIENCE AG Address before: 50 Alfred Nobel Street, Monheim, Rhine, Germany 40789 Patentee before: BAYER INTELLECTUAL PROPERTY GmbH |
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| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20120718 |